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1.
Copper complexes: [Cu(phen)(L-Ser)(H2O)Cl] (1), [Cu(phen)(Gly)(H2O)]Cl·3H2O (2), [Cu(phen)(L-Ala)(H2O)]Cl·H2O (3), [Cu(phen)(L-Phe)(H2O)]Cl·2.5H2O (4), Cu(phen)2Cl2·6H2O (5) (phen = 1,10-phenanthroline) were synthesized and characterized. The structure of 1 was characterized by X-ray crystallography and showed in a triclinic system with space group P1, a = 6.8953(15) Å, b = 10.737(2) Å, c = 11.894(3) Å, α = 110.395(3)°, β = 94.183(4)° and γ = 100.540(3)°. The antibacterial activities on Escherichia coli (E. coli) of these five copper complexes and CuCl2 (6) were investigated by microcalorimetry. By analyzing the obtained metabolic thermogenic data and curves, crucial parameters such as rate constant of bacterial growth (k), half inhibitory concentration (IC50), and generation time (tG) were determined. All these copper complexes could stimulate the growth of the E. coli at their lower concentration. At their higher concentration they all showed antibacterial action. The inhibition on E. coli was 5 > 1 ≈ 2 ≈ 3 ≈ 4 > 6. And the antibacterial mechanism was discussed preliminarily.  相似文献   

2.
ESIMS reveals that methanol solutions of 1:1, 1:2 and 1:3 mixtures of Zn(ClO4)2 · 6H2O and 1,10-phenanthroline (phen) generate [Zn(phen)(OH)]+, [Zn(phen)(H2O)4(OH)]+, [Zn(phen)2(H2O)(OH)]+and [Zn(phen)2(H2O)4(OH)]+ ions in the gas phase. DFT calculations at the B3LYP/LanL2DZ level show that zinc is planar tricoordinate in [Zn(phen)(OH)]+ and the cis configuration is more stable than the trans one for the hexacoordinate ion [Zn(phen)2(H2O)(OH)]+. DFT calculations also show that the [Zn(phen)(H2O)4(OH)]+ and [Zn(phen)2(H2O)4(OH)]+ ions are actually [Zn(phen)(H2O)(OH)]+ · 3H2O and [Zn(phen)2(H2O)(OH)]+ · 3H2O containing extended motifs of H-bonded water clusters. The aqua species corresponding to the monohydroxo ions are acidic. Their acid dissociations are modeled collectively by equilibrium (see below) where other ligands around Zn are not specified. An attempt is then made to estimate Ka
  相似文献   

3.
The nickel(II) complexes of the compositions [Ni(hmidtc)(bpy)2]ClO4 (I), [Ni(hmidtc)(phen)2]ClO4 (II), [Ni(hmidtc)(phen)2]SCN (III), [Ni(hmidtc)(phen)2]PF6 (IV), [Ni(hmidtc)(phen)2]BPh4 (V), [Ni(hmidtc)(phen)2]AcO·2H2O (VI) and [Ni(hmidtc)(phen)2]Br·H2O (VII), involving a combination of one hexamethyleneimine-dithiocarbamate anion (hmidtc) and two bidentate N,N-donor ligands (2,2′-bipyridine (bpy) for I or 1,10-phenanthroline (phen) for II-VII), have been prepared. The compounds were characterized by elemental analysis, molar conductivity measurements, UV-Vis and IR spectroscopy, magnetochemical measurements and thermal analysis. A single-crystal X-ray analysis of the complex I revealed a distorted octahedral geometry with the nickel(II) ion coordinated by four nitrogen atoms (from two bidentate-coordinated bpy molecules) and two sulfur atoms (from one bidentate-coordinated hmidtc anion), together giving an NiN4S2 donor set.  相似文献   

4.
Three novel ternary copper(II) complexes, [Cu2(phen)2(l-PDIAla)(H2O)2](ClO4)2·2.5H2O (1), [Cu4(phen)6(d,l-PDIAla)(H2O)2](ClO4)6·3H2O (2) and [Cu2(phen)2(d,l-PDIAla)(H2O)](ClO4)2·0.5H2O (3) (phen = 1,10-phenanthroline, H2PDIAla = N,N’-(p-xylylene)di-alanine acid) have been synthesized and structurally characterized by single-crystal X-ray crystallography and other structural analysis. Spectrometric titrations, ethidium bromide displacement experiments, CD (circular dichroism) spectral analysis and viscosity measurements indicate that the three compounds, especially the complex 3, strongly bind to calf-thymus DNA (CT-DNA). The intrinsic binding constants of the ternary copper(II) complexes with CT-DNA are 0.89 × 105, 1.14 × 105 and 1.72 × 105 M−1, for 1, 2 and 3, respectively. Comparative cytotoxic activities of the copper(II) complexes are also determined by acid phosphatase assay. The results show that the ternary copper(II) complexes have significant cytotoxic activity against the HeLa (Cervical cancer), HepG2 (hepatocarcinoma), HL-60 cells (myeloid leukemia), A-549 cells (pulmonary carcinoma) and L02 (liver cells). Investigations of antioxidation properties show that all the copper(II) complexes have strong scavenging effects for hydroxyl radicals and superoxide radicals.  相似文献   

5.
Two ruthenium nitrosyl bis-pyridyl/biscarboxamido compounds, [Ru(NO)(bpp)Cl · 2H2O] [bpp = N,N′-bis(2-pyridinecarboxamide)-1,3-propane dianion] and [Ru(NO)(bpe)Cl · 2H2O] [bpe = N,N′-(bis-2-pyridinecarboxamide)-1,2-ethane dianion] have been characterized by 1H NMR, 13C{1H} NMR, and IR spectroscopies, electrospray ionizaton mass spectrometry, and X-ray crystallography.  相似文献   

6.
1,10-Phenanthroline hydrogen phthalato manganese(II) dimer [Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1), monomeric phenanthroline phthalato manganese(II) monomer [Mn(phth)(phen)2(H2O)] · 2.5H2O (2), 2,2′-bipyridine phthalato manganese(II) polymer [Mn(phth)(bpy)(H2O)2]n (3) and 1,10-phenanthroline maleato polymer [Mn(male)(phen)(H2O)2]n · 2nH2O (4) (H2phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn-syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer [Mn(male)(phen)]n · nH2O (5) with dehydration in warm solution.  相似文献   

7.
The dinuclear and trinuclear copper(II) complexes [Cu2(L)(OH)(ClO4)(phen)(H2O)]ClO4 · [Cu2(L)(OH)(ClO4)2(phen)(CH3OH)] (1) and [Cu3(L)2(OH)2(H2O)2](NO3)2 (2) (HL=2-[2-(α-pyridyl)ethyl]imino-3-butanone oxime and phen=1,10-phenanthroline) were prepared and their crystal structures have been determined by X-ray crystallography. Complex 1 is composed of [Cu2(L)(OH)(ClO4)(phen)(H2O)]ClO4 (1a) and [Cu2(L)(OH)(ClO4)2(phen)(CH3OH)] (1b). In 1a and 1b, one oximato of L and one hydroxo group bridge two copper(II) ions. The linear trinuclear cation [Cu3(L)2(OH)2(H2O)2]2+ in 2 is centrosymmetric, and one oximato and one hydroxo group bridge the central and terminal copper(II) ions. The strong antiferromagnetic interactions within the dinuclear and trinuclear complexes 1 and 2 have been observed (2J=∼−900 cm−1 for 1 and 2, respectively, H=−2JS1·S2).  相似文献   

8.
Three ternary zinc complexes of the open chain polycarboxylic acid, tricarballylic (1,2,3-propane-tricarboxylic) acid (PTCH3) have been isolated and characterized with crystallographic and physicochemical techniques. [Zn(PTCH)(phen)(H2O)]2 · 4H2O (1) (where phen = 1,10-phenanthroline) has a unique dinuclear structure, while [Zn(PTCH)(bpy)]n · 3nH2O (2) and [Zn(PTCH)(epy)]n · 4nH2O (3) (where bpy = 4,4′-bipyridine and epy = 1,2-bis(4-pyridine)ethane) have 2D polymeric structures. The bis-deprotonated ligand, in all three complexes, uses for coordination only two oxygen atoms, which belong to the same carboxylate in 1, and to two different carboxylates in 2 and 3.  相似文献   

9.
The heterotrimetallic complex, [{LCuMn(H2O)}{Cr(phen)(C2O4)2}](ClO4) · H2O (1), has been obtained by assembling heterobinuclear cations, [LCuMn]2+, with [Cr(phen)(C2O4)2] ions (H2L is the compartmental Schiff-base resulting from the stepwise condensation of 2,6-diformyl-p-cresol with ethylenediamine and diethylenetriamine). The copper(II) and manganese(II) ions are hosted into the compartments of the macrocyclic ligand. [Cr(phen)(C2O4)2] acts as a ligand, being coordinated through one oxalato oxygen atom to the apical position of the square pyramidal copper(II) ion. The cryomagnetic investigation of 1 reveals an antiferromagnetic interaction between CuII and MnII within the compartmental ligand (J = −39 cm−1). The interaction between CuII and CrIII across the oxalato bridge is negligible. The crystal structure of [LCuPb](ClO4)2 · H2O, a useful precursor in obtaining 3d-3d′ complexes, is also reported.  相似文献   

10.
The synthesis and characterization of seven new solid complexes, [Cu(2-MeSnic)2 (phen)] (2-MeSnic = 2-methylthionicotinate, phen = 1,10-phenanthroline), [CuX2(bipy)(H2O)] (X = 2-MeSnic or nic (nicotinate), bipy = 2,2′-bipyridine), [Cu(isonic)2(bipy)(H2O)] · H2O (isonic = isonicotinate), [Cu(bipy)2(H2O)](2-MeSnic)2 · 3H2O, [Cu(phen)2(H2O)](isonic) 2 · 2H2O and [Cu(phen)2(H2O)](nic)2 · 3H2O, are reported. The composition and stereochemistry as well as the mode of ligand coordination have been determined by elemental analysis, IR, electronic and EPR spectra. The carboxyl group of the pyridinecarboxylate anions coordinates to the Cu(II) atom as an unidentate or as a chelating ligand. The EPR spectra of studied complexes are monomeric except for the spectrum of [Cu(2-MeSnic)2(bipy)(H2O)], which shows triplet state feature. Half-field transition, observed for [Cu(2-MeSnic)2(bipy)(H2O)], [Cu(bipy)2(H2O)](2-MeSnic)2 · 3H2O and [Cu(phen)2(H2O)](nic)2 · 3H2O, was used to estimate the interspin copper-copper distances. In all cases, the available evidence supports square-pyramidal environment about the copper(II) atom, which is confirmed by crystal and molecular structure of one of the products, namely [Cu(2-MeSnic)2(bipy)(H2O)]. The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi.  相似文献   

11.
A new zinc(II) compound, [Zn2(Hsal)4(4,4′-bpe)2] · [Zn(Hsal)2(4,4′-bpe)(DMF)(H2O)] · CH3OH (1) (Hsal = salicylate and 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethylene) has been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The crystal structure consists of three independent moieties: [Zn2(Hsal)4(4,4′-bpe)2], [Zn(Hsal)2(4,4′-bpe)(DMF)(H2O)], and non-coordinated CH3OH molecule. In the compound two independent moieties which are connected by 4,4′-bpe to form 1-D chains, respectively, are further expended to accomplish 2-D network through hydrogen-bonding interactions between non-coordinated methanol and coordinated water molecule or carboxylate oxygen atoms of Hsal ligands.  相似文献   

12.
Two tetranuclear copper(II) complexes with long rigid Schiff-base ligands [Cu4(bmsbd)2]·2DMF [H2bmsbd = N,N′-bis-(3-methoxy-salicylidene)benzene-1,4-diamine] (1) and [Cu4(besbd)2]·DMF·5H2O [H2besbd = N,N′-bis-(3-methoxy-salicylidene)benzene-1,4-diamine] (2) have been synthesised and characterized. Single X-ray diffraction analysis reveals that both complexes exhibit interesting [2 × 2] molecular grid-like configuration assembled by four organic ligands in a head-to-tail mode to bind four copper(II) ions. Magnetic property investigations reveal weak antiferromagnetic interaction viaσ-bond pathway of long rigid Schiff-base ligand between the neighboring copper(II) ions in both complexes.  相似文献   

13.
Efficient cleavage of supercoiled pBR322 DNA by X-ray crystallographically characterized complex, [UO2(phen)(aba)(OC2H5)] (phen = 1,10-phenanthroline; aba = 4-dimethylamino benzoate) has been observed on irradiation with UV (350 nm) or visible light without any external additives through a mechanistic pathway involving singlet oxygen. This complex having 1,10-phenanthroline as an intercalator/binder to supercoiled DNA and N,N-(dimethylamino)benzoate as a chromophore.  相似文献   

14.
Several new Cu-hippurate derivative-phenanthroline ternary complexes have been prepared. The X-ray structure of one of them, [Cu(hip)(phen)2]+·(hip) (2) (where hip is hippurate and phen is 1,10-phenanthroline) has been solved. The structure of this new compound shows important differences (3D-pattern) to other similar related complexes (2D-pattern). A study of the biological activity of [Cu(hip)(phen)2]+·(hip)·2H2O (2), [Cu(BGG)(phen)2]+·(BGG)·6H2O (3), [Cu(BIGG)2(phen)](H2O) (4) and [Cu(I-hip)(bpy)2]+·(I-hip)·3.5H2O (5) (where I-hip is ortho-iodohippurate, BGG corresponds to benzoylglycilglycine, and BIGG is ortho-iodobenzoylglycilglycine) is included and compared with the anti-proliferative activity of [Cu(I-hip)(phen)2]+·(I-hip)·7H2O (1) previously described, resulting in a greater cytotoxic activity of the compounds with 1,10-phenanthroline instead of those with 2,2′-bipyridyl, in the same way that removing iodine substitution or lengthening the peptidic chain diminishes the activity of compounds compared with 1. The presence of an ortho-iodine group and the direct bond between Ar-CO and glycine moieties yield to the best results.  相似文献   

15.
A 2D porous material, Cu3(tmen)3(tma)2(H2O)2 · 6.5H2O [tmen = N,N,N′,N′-tetramethylethane-1,2-diamine; tmaH3 = 1,3,5-benzenetricarboxylic acid/trimesic acid], has been synthesized and characterized by X-ray single crystal analysis, variable temperature magnetic measurements, IR spectra and XRPD pattern. The complex consists of 2D layers built by three crystallographically independent Cu(tmen) moieties bridged by tma anions. Of the three copper ions, Cu(1) and Cu(2) present distorted square pyramidal coordination geometry, while the third exhibits a severely distorted octahedral environment. The Cu(1)(tmen) and Cu(2)(tmen) building blocks bridged by tma anions give rise to chains with a zig-zag motif, which are cross-connected by Cu(3)(tmen)-tma polymers sharing metal ions Cu(2) through pendant tma carboxylates. The resulting 2D architecture extends in the crystallographic ab-plane. The adjacent sheets are embedded through the Cu(3)(tmen)-tma chains, leaving H2O-filled channels. There are 6.5 lattice water molecules per formula unit, some of which are disordered. Upon heating, the lattice water molecules get eliminated without destroying the crystal morphology and the compound rehydrated reversibly on exposure to humid atmosphere. Magnetic data of the complex have been fitted considering isolated irregular Cu3 triangles (three different J parameters) by applying the clumag program. The best fit indicates three close comparable J parameters and very weak antiferromagnetic interactions are operative between the metal centers.  相似文献   

16.
The antibacterial mechanisms of Cu(phen)2Cl2·6H2O, [Cu(phen)(Gly)(H2O)]Cl·3H2O, [Cu(phen)(l-Ser)(H2O)Cl] (1,10-phenanthroline (phen)) on Escherichia coli were investigated. In the inductively coupled plasma atomic emission spectroscopy experiments, it showed that lipophilic phen ligand can cause elevation of intracellular copper, but intracellular copper is not the decisive factor. The UV–vis and gel electrophoresis experiments reveal that the DNA binding and cleavage activity are decisive factors for the antibacterial action of these compounds. It is revealed by the cyclic voltammetry experiments that the redox potential was bound to the cleave activity.  相似文献   

17.
A new one-dimensional (1D) copper(II) complex, [Cu2(dpk · CH2O)(N3)3]n (dpk · CH2OH = unimethylated diol of di-2-pyridyl ketone) (1), has been synthesized and characterized. X-ray crystal structure study reveals that 1 is composed of 1D copper(II) chain with alternating double EO-azido bridges and mixed EO-azido/alkoxo double bridges. The magnetic determination indicates that ferromagnetic interaction dominates in this new 1D S = 1/2 system.  相似文献   

18.
A series of copper(II) complexes, i.e. Cu2LCl4, CuLCl2·H2O and [Cu2L2Cl4]·2MeCN (8), based on a new potentially polytopic ligand, 3,5-bis(4,6-dimethylpyrimidin-2-yl)-4H-1,2,4-triazol-4-amine (3b, L), have been synthesized. The crystal structures of L and [Cu2L2Cl4]·2MeCN were studied by X-ray single crystal analysis. The dinuclear compound [Cu2L2Cl4]·2MeCN represents the first example of structurally characterized metal complexes with 3,5-di(pyrimidin-2-yl)-4H-1,2,4-triazol-4-amines. Both copper atoms have distorted tetragonal-pyramidal 3N + 2Cl environment. Surprisingly, in contrast to the complexes based on 3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-amine (pyridinyl analog of L), the compound [Cu2L2Cl4]·2MeCN adopts a dinuclear trans-(N′,N1,N2)2 double bridging binding mode which is due to tridentate coordination of two L molecules linking two copper atoms through N1,N2-triazole and N′-pyrimidine atoms. It seems to be reasonable that it is methyl groups in pyrimidinyl moiety that obstruct the expected dinuclear (N′,N1,N2,N″)2 double bridging coordination being one of the most common for 4-substituted 3,5-di(pyridin-2-yl)-4H-1,2,4-triazoles and 3,5-di(pyridin-2-yl)-1,2,4-triazolates. Due to π-π stacking interactions, molecules of Cu2L2Cl4 in the structure of [Cu2L2Cl4]·2MeCN form 1D chains.  相似文献   

19.
One lead(II) coordination polymer, {[Pb(fum)(phen)]·2H2O}n (fum = fumarate, phen = 1,10-phenanthroline), was synthesized through the self-assembly of the lead(II) ion with the mixed fum and phen ligands and characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis, X-ray analysis and solid state photoluminescence spectrum. The compound shows a center-symmetrical dinuclear-based 2D architecture and further assembles into porous 3D supramolecular framework with 1D channel via interlayer π-π stacking interactions. The six-coordinated lead atoms in the complex show hemidirected geometry. The compound exhibits photoluminescence with the maximum emission located in UV region.  相似文献   

20.
The use of succinamic acid (H2sucm) in Cu(ClO4)2·6H2O/N,N′-donor [2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4′-dimethyl-2,2′-bipyridine (dmbpy), 4,4′-bipyridine (4,4′-bpy)] reaction mixtures yielded compounds [Cu2(Hsucm)3(bpy)2](ClO4)·0.5MeOH (1·0.5MeOH), [Cu2(Hsucm)(OH)(H2O)(bpy)](ClO4)2 (2), [Cu4(Hsucm)5(dmbpy)4]n(ClO4)3n·nH2O ·0.53nMeOH (3·nH2O·0.53nMeOH), [Cu2(Hsucm)2(dmbpy)2(H2O)2](ClO4)2·2H2O (4·2H2O), [Cu2(Hsucm)2(phen)2(H2O)2](ClO4)2·1.8MeOH (5·1.8MeOH), [Cu2(Hsucm)2(phen)2(MeOH)2](ClO4)2·MeOH (6·MeOH) and [Cu(Hsucm)2(H2O)(4,4′-bpy)]n (7). The succinamate(−1) ligand exists in five different coordination modes in the structures of 1-7, i.e. the common syn, syn μ2OO′ in 1-6, the μ22O in 1, the μ22OO′ in 1, the μ32O2O′ in 3, and the monodentate κO in 7. The primary amide group of Hsucm remains uncoordinated and participates in intra- and intermolecular hydrogen bonding interactions leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm ligands. The thermal decomposition of representative complexes was monitored by TG/DTG and DTA measurements.  相似文献   

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